Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH3) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi0/Bi3+ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900 °C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH3 yield rate and remarkable Faradaic efficiency of 15.10 ± 0.43% at −0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p‐filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential‐determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis. An oxidation state modulation strategy is proposed to boost nitrogen reduction to ammonia. As a proof‐of‐concept, the surface oxidation of Bi species is tuned with the less occupied p orbital, which leads to stronger adsorption of *NNH and lower ΔG of the potential‐determining step. By optimizing Bi surface oxidation, superior nitrogen reduction reaction performance of Faradaic efficiency of 15.10 ± 0.43% is achieved.